Intermolecular forces, liquids and solids

States of Matter: Gas, liquid, solid To understand properties of the various states of matter, one has to examine attractive forces between molecules (intermolecular forces)

Intermolecular forces
ion ion ion dipole ion induced dipole dipole dipole dipole induced dipole induced dipole induced dipole van der Waals forces
van der Waals' forces include all intermolecular forces that act between electrically neutral molecules.

ionic bonds solvation

solutions of salts

polar solvents

Hydrogen bonds a special type of dipole dipole attractive force

Structure of ice

Hydrogen bonding in proteins and nucleic acids

Dispersion forces - attractive forces that result from temporary

dipoles induced in an atom or molecule. Ion induced dipole attractive force

Polarizability:

increases with size of atom fluorine very nonpolarizable (hard) Iodine very polarizable (soft)

Dipole induced dipole attractive force

Induced dipole induced dipole attractive force

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Properties of Liquids
Surface tension and viscosity

Surface tension Classical definition: the tendency of a liquid to minimize its surface. Quantitative definition: amount of energy required to stretch or increase the surface by a unit area.

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Capillary action is another manifestation of surface tension. Example of water rising in a narrow glass tube. Two forces (cohesion and adhesion) are involved Cohesion: attractive forces between molecules of liquids Adhesion: attractive forces between the liquid and the glass

When adhesion is greater than cohesion, the liquid (eg. water) rises in the capillary tube

When adhesion is smaller than cohesion, a depression of the liquid (eg. Hg) in the capillary tube results

The meniscus in the tube of water is concave whereas that in the tube of mercury is convex.

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Viscosity a measure of a liquids resistance to flow

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Phase changes Liquid-vapor equilibrium

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Vapor pressure
is characteristic property of a particular substance; increases with temperature

Heat of vaporization and boiling point

related to strength of intermolecular forces

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Boiling point: temperature at which vapor pressure of substance equals external pressure. Normal boiling point: boiling point when external pressure equals 1 atmosphere.

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Liquid-solid equilibrium Melting point: temperature at which solid and liquid coexist in equilibrium. Normal melting point: melting point when external pressure equals 1 atmosphere.

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Solid-vapor equilibrium

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Phase diagram

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Physical properties of solutions (Chapter 13 in the textbook)

A solution is a homogeneous mixture of two or more substances in a single phase Saturated solution: contains the maximum amount of a solute in a given solvent at a specific temperature. Unsaturated solution: contains less solute than it has the capacity to dissolve. Supersaturated solution: contains more solute than is present in a saturated solution.

A molecular view of the solution process

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An old saying like dissolves like polar solutes dissolve in polar solvents; nonpolar solutes dissolve in nonpolar solvents
CCl4 and C6H6 are completely soluble in each other in all proportions (miscible). Forces of intermolecular attraction in CCl4 are weak. Forces of intermolecular attraction in C6H6 are weak. Forces of intermolecular attraction between CCl4 and C6H6 are also weak.

ethanol and water are completely soluble in each other in all proportions (miscible). Hydrogen bonding in ethanol. Hydrogen bonding in water. Hydrogen bonding in a solution of ethanol in water.

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Nonpolar solute Polar solvent: attractive forces between solute and solvent are not sufficient to overcome solvent-solvent attractive forces. Nonpolar solvent: all attractive forces are weak; Ho is small and tendency toward disorder is more important than energy.

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Polar solute Polar solvent: attractive forces between solute and solvent are sufficient to overcome solute-solvent attractive forces and solventsolvent attractive forces. Nonpolar solvent: attractive forces between solute and solvent are not sufficient to overcome solute-solute attractive forces.

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Effect of temperature on solubility

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Effect of pressure on solubility of gases Pressure has little effect on solubility of solids or liquids in liquids

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Colligative properties
Colligative: (,,)

depend on number of particles of a solute in solution and not on the nature of the solute vapor pressure lowering boiling point elevation freezing point depression osmotic () pressure vapor pressure lowering: The vapor pressure of a solution containing a nonvolatile solute is always less than that of the pure solvent. Driving force for vaporization increases in disorder in going from liquid to vapor phase. Solution is more disorder than pure liquid, so driving force for vaporization is less for solution.

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Boiling point elevation and freezing point depression

Since its vapor pressure at a particular temperature is depressed, the boiling point of a substance must be higher when something is dissolved in it than when it is pure. For the same reason, the freezing point of a substance must be lower when something is dissolved in it than when it is pure.

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Osmosis Osmosis is the movement of solvent molecules through a semipermeable membrane from a region of lower solute concentration to a region of higher solute concentration. The effect is to remove solvent from the more dilute solution to the more concentrated solution.

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Colligative properties of electrolyte ( solutions ) Colligative properties are properties that depend on the number of solute particles in solution and not on the nature of the solute particles. Substances that produce ions give a greater concentration of particles than expressed by the molar concentration of the solute.

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Crystal structures of solids

Types of crystalline solids determined by kinds of forces that hold the particles together

Ionic crystals Molecular crystals Covalent crystals Metallic crystals Characteristics and examples

ionic bonds van der Waals forces covalent bonds metallic bonds

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An important concept in describing crystal structures Unit cell The unit cell is a component of crystal that reproduces the whole when stacked together repeatedly. To represent the crystal structure with an infinite extension in the three dimensional directions? Note: those atoms in the boundary are shared with other repeating unit. The structures of crystalline solids are best described in terms of the unit cell.

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A two-dimensional solid and two choices of unit cell. The entire crystal is reproduced by translational displacements of either unit cell, but (a) is generally preferred because it displays the maximum symmetry of the structure, but (b) does not.

From the two-dimensional case, we learn that for a given periodical arrangement, the number of choices in unit cell can be

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The close packing of spheres

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Two major types of close packing

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Cubic close packing (also called face centered close packing) abbreviation: ccp or fcc

Pattern:

ABCABCABC

Choosing unit cell for fcc (or ccp) Choice 1: corners and face-centered Number of balls in a unit cell = ?

facecentered cubic

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Choice 2:

cuboctahedron

edge and body centered Number of balls in a unit cell = ?

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Hexagonal close packing Pattern: ABABAB

hcp

Number of balls in a unit cell = ?

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Table: The most stable crystal structures assumed by the elements in their solid phase He hcp C N O F Ne d hcp sc - ccp Si P S Cl Ar d sc or tet ccp Ge As Se Br Kr d rh hcp or ccp Sn Sb Te I Xe tet rh hcp or ccp Pb Bi Po At Rn ccp rh mono - ccp

Li bcc Na bcc K bcc Rb bcc Cs bcc

Be hcp Mg hcp Ca Sc Ti V Cr ccp hcp hcp bcc bcc Sr Y Zr Nb Mo ccp hcp hcp bcc bcc Ba La Hf Ta W bcc hcp hcp bcc bcc

Mn bcc Tc hcp Re hcp

Fe bcc Ru hcp Os hcp

Co Ni hcp ccp Rh Pd ccp ccp Ir Pt ccp ccp

Cu Zn ccp hcp Ag Cd ccp hcp Au Hg ccp rh

B rh Al ccp Ga sc In tet Tl hcp

Note: sc = simple cubic, tet = tetragonal, rh = rhombohedral, d = diamond or = orthorhombic, mono = monoclinic

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Structural characteristics of fcc and hcp Holes in close-packed structures

See example 3.3 for the calculation of the size of an octahedral hole

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Tetrahedral site

FCC
Octahedral site

HCP

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no. of holes surrounding a ball no. of balls : no. of An A hole is shared by hole is shared by holes : no. of balls balls. holes = ?

Ionic solids
Many ionic solid structures can be regarded as derived from arrays in which the anions (sometimes the cations) stack together in fcc or hcp (or others) patterns and the counter ions occupy the octahedral and tetrahedral holes in the close packing.

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MX structures Rock salt structure

packing type ? hole occupancy ? coordination number for each cation (or anion)?

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Zinc blende (ZnS) structure

packing type ? hole occupancy ? coordination number for each cation (or anion)?

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Octahedral (Oh) sites

Tetrahedral (Td) sites

1 at the center

12 edge sites
(each shared by 4 cells)

Net 4 Oh sites/unit cell

Net 8 Td sites/unit cell

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Cesium chloride structure

packing type ? hole occupancy ? coordination number for each cation (or anion)?

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MX2 structures Fluoride (CaF2)

packing type (Ca) ? hole occupancy ? coordination number for cation and anion?

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More complicated structures: Perovskite structure ABO3 (CaTiO3)

Ca and O form close packing. holes. Ti's fill % of the Coordination number of Ti: Coordination number of Ca: Coordination number of O:

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Relationship between some important structures

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